JP4228000B2 - Laminated molded body - Google Patents

Description

  The present invention relates to a laminated molded body that can be suitably used as an exterior building material using a stretched thermoplastic polyester resin sheet as a core material.

  Vinyl chloride resins are widely used as materials for building members because they are excellent in water resistance, flame retardancy, mechanical properties, etc., and are relatively inexpensive. For example, rain gutters are generally formed by extrusion of a hard vinyl chloride resin.

  However, the linear expansion coefficient of hard vinyl chloride resin moldings is as large as 7.0 x 10-5 (1 / ° C). It was necessary to connect with a joint that can absorb or to make the end free, but if the length of the rain gutter to be constructed was long, there were many joints and outlets, and the appearance was bad. .

For this reason, various studies have been made on rain gutters having a low coefficient of linear expansion. For example, it consists of a vinyl chloride resin composition in which 20 to 35 parts by weight of mica, 20 to 40 parts by weight of calcium carbonate, and 5 to 15 parts by weight of processing aids are added to 100 parts by weight of vinyl chloride resin. A vinyl chloride-based resin gutter (see, for example, Patent Document 1) is proposed.
Japanese Patent No. 2905260

  The above gutters are made of vinyl chloride resin with mica and calcium carbonate added to lower the linear expansion coefficient of gutters, but are mainly made of vinyl chloride resin, and the amount of mica and calcium carbonate added is low. If the amount is small, the linear expansion coefficient is still high, and if the amount added is large, the impact resistance and durability of the rain gutter are lowered.

In addition, rain gutters impregnated with glass fiber as a reinforcing material or laminated with thin metal plates have been proposed. For example, a composite sheet composed of a thermoplastic resin and reinforcing fibers is shaped to the required cross-sectional shape, and the thermoplastic resin is extrusion-coated on the surface, and the composite sheet is reinforced at least on the shaped part. A composite molded product characterized in that short fibers are randomly oriented (see, for example, Patent Document 2), a metal thin plate as a core material, and a synthetic resin is coated on both surfaces of the core material to form a sheet material, In the rain gutter formed by pressing the bending jig distal end against the sheet material to be bent into a substantially U-shaped cross section, the bending jig distal end is located at the bending position of the synthetic resin on the inner surface side. A rain gutter (for example, refer to Patent Document 3) characterized by providing a groove to be guided has been proposed.
Japanese Patent Laid-Open No. 11-19998 Japanese Patent Laid-Open No. 9-297883

  However, the former gutter consists of a thermoplastic resin and reinforcing fibers. A composite sheet in which short fibers are randomly oriented must be created and shaped into the required cross-sectional shape, and then the thermoplastic resin must be extrusion coated on the surface. It is difficult to manufacture, and the glass fiber powder is scattered when cut during construction of rain gutters, so that workability is poor, there is a problem in environmental hygiene, and there is a problem in disposal. .

  The latter rain gutter is laminated with a thin metal plate as a core material, so that it is heavy and difficult to cut, and the metal thin plate is exposed at the end of the gutter, and rust is generated over time. In addition, there is a drawback that durability is lowered by corrosion.

Further, as a rain gutter having a low coefficient of linear expansion without using a core material or glass fiber made of a metal thin plate, for example, a polyolefin having an average linear expansion coefficient of 20 to 80 ° C. of 5 × 10 ⁻⁵ (/ ° C.) or less. After the low molecular weight compound that dissolves the polyolefin was adhered to the surface of the stretched material, the polyolefin stretched material was adhered by pressing and heating, and the average linear expansion coefficient at 20 to 80 ° C. was 5 × 10 ⁻⁵ (/ ° C) The following is a polyolefin molded body (for example, see Patent Document 4), after extruding a thermoplastic resin, and further stretching and stretching the extruded resin to orient the molecules in one direction, A synthetic resin rain gutter (for example, see Patent Document 5) characterized in that the linear expansion coefficient of the plastic synthetic resin is 6 × 10 ⁻⁵ / ° C. or less and the thickness is greater than 0.5 mm has been proposed.
JP-A-10-291250 Japanese Patent Laid-Open No. 2002-285685

  However, the former rain gutter is a highly stretched sheet of polyolefin stretched material of 20 to 40 times, and has the disadvantage of being easily broken along the stretch direction and having poor impact resistance. When trying to laminate with vinyl resin, AES resin or the like, polyolefin has a lower melting point than these resins, so that the stretched state of the polyolefin collapses and the linear expansion coefficient becomes high.

  Further, since the latter rain gutter is simply a stretched gutter that has been stretched, it has the disadvantage of being easily broken along the stretch direction and having poor impact resistance.

  In view of the above-mentioned drawbacks, the object of the present invention is a laminated molded body having a low coefficient of linear expansion, light weight, excellent impact resistance, durability, workability, productivity, etc., particularly as exterior building materials such as rain gutters. An object of the present invention is to provide a laminated molded body that can be suitably used.

Molded laminate according to claim 1 is a non-crystalline state thermoplastic polyester resin sheet, the temperature of the glass transition temperature + 20 ° C. of glass transition temperature of -20 ° C. ~ thermoplastic polyester resin of the thermoplastic polyester resin The thermoplastic resin layer is laminated | stacked on both surfaces of the extending | stretching thermoplastic polyester-type resin sheet (except the case where it uniaxially stretches at a temperature higher than the temperature of this roll ) draw-drawn and stretched between a pair of these rolls .

  The molded article according to claim 2, wherein the amorphous polyester sheet has a crystallinity of less than 10% as measured by a differential scanning calorimeter. It is.

  The laminated molded article according to claim 3 is a laminated molded article according to claim 1 or 2, wherein the stretched thermoplastic polyester resin sheet has a stretch ratio of 2 to 9 times.

  The laminated molded article according to claim 4, wherein two or more stretched thermoplastic polyester resin sheets are laminated so that the stretching directions are substantially the same. This is a laminated molded body.

  The laminated molded article according to claim 5 is characterized in that two or more stretched thermoplastic polyester resin sheets are bonded with a hot-melt adhesive having a melting point lower than that of the thermoplastic polyester resin. It is a laminated molded object of any one of Claims 1-4.

  The laminated molded article according to claim 6 is the laminated molded article according to claim 5, wherein the hot melt adhesive is fused by an ultrasonic welder.

  The laminated molded article according to claim 7, wherein two or more stretched thermoplastic polyester resin sheets are formed of a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive. It is adhere | attached with the 1 type (s) or 2 or more types of adhesives chosen from these, It is a laminated molded object of any one of Claims 1-4 characterized by the above-mentioned.

  The laminated molded article according to claim 8 is characterized in that a woven fabric and / or a nonwoven fabric is laminated between two or more stretched thermoplastic polyester resin sheets. It is a laminated molding of description.

  The laminated molded article according to claim 9, wherein a woven fabric impregnated with a hot melt adhesive having a melting point lower than the melting point of the thermoplastic polyester resin between two or more stretched thermoplastic polyester resin sheets and The laminated molded product according to any one of claims 1 to 4, wherein the nonwoven fabric is laminated and bonded.

  The laminated molded article according to claim 10 is the laminated molded article according to claim 9, wherein the hot melt adhesive is fused by an ultrasonic welder.

  The laminated molded article according to claim 11 includes a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive between two or more stretched thermoplastic polyester resin sheets. The woven fabric and / or the nonwoven fabric impregnated with one or two or more kinds of adhesives selected from the group consisting of the above-mentioned groups are laminated and adhered. It is a laminated molded body.

  The laminated molded article according to claim 12, wherein the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are bonded with a hot melt adhesive having a melting point lower than that of the thermoplastic polyester resin. The laminated molded body according to any one of claims 1 to 11.

  The laminated molded article according to claim 13 is the laminated molded article according to claim 12, wherein the hot melt adhesive is fused by an ultrasonic welder.

  The laminated molded article according to claim 14, wherein the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer comprise a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive. It is adhere | attached with 1 type or 2 or more types of adhesives chosen from the group, It is a laminated molded object of any one of Claims 1-11 characterized by the above-mentioned.

  The laminated molded body according to claim 15, wherein a woven fabric and / or a nonwoven fabric is laminated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. It is a laminated molding of 1 item | term.

  The laminated molded article according to claim 16, wherein the hot-melt adhesive having a melting point lower than the melting point of the thermoplastic polyester resin is impregnated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. The laminated molded article according to any one of claims 1 to 11, wherein the nonwoven fabric is laminated and bonded.

  The laminated molded body according to claim 17, wherein the hot-melt adhesive is fused by an ultrasonic welder.

  The laminated molded article according to claim 18, wherein a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive are provided between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. The woven fabric and / or the nonwoven fabric impregnated with one or two or more types of adhesives selected from the group consisting of the above-mentioned groups are laminated and adhered. This is a laminated molded body.

  The laminated molded body according to claim 19 is the laminated molded body according to any one of claims 1 to 18, wherein the laminated molded body is an exterior building material.

  Examples of the thermoplastic polyester resin used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyglycolic acid, poly (L-lactic acid), poly (3-hydroxybutyrate), poly ( 3-hydroxybutyrate / hydroxyvalerate), poly (ε-caprolactone), polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate / lactic acid, polybutylene succinate / carbonate, polybutylene succinate Nate / terephthalate, polybutylene adipate / terephthalate, polytetramethylenadipate / terephthalate, polybutylene succinate / adipate / terephthalate, etc. Polyethylene terephthalate is preferable.

  Further, if the intrinsic viscosity is too low, drawdown is likely to occur at the time of producing the sheet, and if it is too high, the mechanical strength (particularly the elastic modulus) does not increase even if stretched, so 0.6 to 1.0 is preferable.

  The thickness of the thermoplastic polyester resin sheet is not particularly limited, but if it is less than 0.1 mm, the sheet thickness after stretching becomes too thin, and the strength during handling may not be sufficiently large. Since it may become difficult, 0.1-5 mm is preferable, More preferably, it is 0.2-3 mm.

  The stretched thermoplastic polyester resin sheet is in an amorphous state. The stretched thermoplastic polyester resin sheet may be in an amorphous state, and the crystallinity thereof is not particularly limited, but the crystallinity measured by a differential scanning calorimeter is preferably less than 10%, More preferably, it is less than 5%.

In the present invention, the thermoplastic polyester resin sheet in the amorphous state is drawn and stretched through a pair of rolls. Drawing and drawing through a pair of rolls is preferable because the thickness after drawing can be freely controlled and wear of a specific part of the drawing die does not occur.

  The temperature of the thermoplastic polyester resin sheet during drawing and drawing is not particularly limited, but it is preferably preheated to a temperature near the glass transition temperature.

The preheating temperature is preferably a glass transition temperature of the thermoplastic polyester resin of −20 ° C. to a glass transition temperature of the thermoplastic polyester resin of + 10 ° C.
This is because the resin sheet may not reach a predetermined temperature if the preheating temperature is too low or too high.

  If the temperature at the time of drawing and drawing is low, the thermoplastic polyester resin sheet is too hard, and even if it is to be drawn, it may be cut first. The thermoplastic polyester resin sheet becomes soft at a high temperature, and the sheet is cut by the tension that pulls out the sheet. Therefore, the glass transition temperature of the thermoplastic polyester resin is -20 ° C. to the thermoplastic resin. The glass transition temperature of the polyester-based resin + 20 ° C., preferably the glass transition temperature of the thermoplastic polyester-based resin to the glass transition temperature of the thermoplastic polyester-based resin + 10 ° C.

  Further, when the amorphous polyester resin sheet in the amorphous state is pulled out, the roll does not need to be rotated. However, especially when the thickness of the thermoplastic polyester resin sheet is thick, the heat storage of the roll by shearing heat generation is required. It is preferable to rotate the sheet in the drawing direction because the temperature of the resulting sheet is likely to increase.

  Therefore, the rotational speed of the roll is preferably substantially the same or lower than the feed speed when the thermoplastic polyester resin sheet is pulled out in the state where the roll is not rotating at the same drawing speed.

  Further, when the thickness of the thermoplastic polyester resin sheet is large (1.5 mm or more), heat generation due to shearing between the roll and the sheet becomes large, and therefore, the rotation speed of the roll is preferably 50 to 100% of the feed speed. . Moreover, when the thickness of the thermoplastic polyester resin sheet is thin, the cooling effect by the roll is great, so the rotation speed of the roll may be slow.

  The draw ratio of the above-described drawing stretching is not particularly limited. However, if the stretching ratio is low, a sheet excellent in tensile strength and tensile elastic modulus cannot be obtained. If the stretching ratio is high, the sheet tends to break during stretching. 2 to 9 times, preferably 2.5 to 8 times.

In the present invention, the case where the drawn and stretched thermoplastic polyester resin sheet is uniaxially stretched at a temperature higher than the pair of roll temperatures of the stretched drawing is excluded .

  The polyester resin of the thermoplastic polyester resin sheet that has been drawn and stretched is highly oriented because molecular chains are highly oriented in a state in which isotropic crystallization and orientation due to heat, which is an impediment to stretching, are suppressed. Although the elastic modulus is excellent, since the degree of crystallinity is low, there is a disadvantage that the orientation is easily relaxed and the elastic modulus is lowered when heated.

Incidentally, the rising temperature of the crystallization peak of polyethylene terephthalate is about 120 ° C., the rising temperature of the melting peak of about 230 ° C..

In the present invention, the drawn and stretched thermoplastic polyester resin sheet may be heat-set in order to further improve the heat resistance.

When the heat setting temperature is lower than the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min, the crystallization of the thermoplastic polyester resin does not proceed, so the heat resistance If the temperature is higher than the rise temperature of the melting peak, the thermoplastic polyester resin dissolves and the stretching (orientation) disappears, and the tensile modulus, tensile strength, etc. decrease, so measure at a heating rate of 10 ° C / min. The rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak in the differential scanning calorimetry curve is preferable .

  Further, when heat-fixing, the stretched thermoplastic polyester resin sheet is stretched if a large tension is applied, and is not tensioned or shrinks in a very small state. It is preferable that the length is not substantially changed, and it is preferable that no pressure is applied to the stretched thermoplastic polyester resin sheet.

That is, the length of the heat-set stretched thermoplastic polyester resin sheet is 0.95 to 1.1 of the length of the stretched thermoplastic polyester resin sheet before heat setting, which is lower than the draw ratio. Thus, it is preferable to heat-set.

Therefore, when the stretched thermoplastic polyester resin sheet is heat-set continuously while moving in the heating chamber with a roll such as a pinch roll, the feed rate ratio of the stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to 0. It is preferably set to be a ratio lower than the drawing draw ratio and heat-set at .95 to 1.1.

  The heating method at the time of heat setting is not particularly limited, and examples thereof include a method of heating with hot air or a heater.

  The time for heat setting is not particularly limited, but is generally 10 seconds to 10 minutes, although it varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the heat setting temperature.

  Furthermore, the range of the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve of the heat-set stretched thermoplastic polyester resin sheet measured at a glass transition temperature to a heating rate of 10 ° C./min. Thus, annealing may be performed in a state where substantially no tension is applied.

  By annealing, the stretched thermoplastic polyester resin sheet has good mechanical properties such as elastic modulus, and even if it is heated to a temperature higher than the glass transition temperature, the mechanical properties such as elastic modulus may decrease. And the shrinkage rate can be kept low.

  In addition, since the stretched thermoplastic polyester resin sheet is stretched when a large tension is applied thereto, it is preferable to anneal the stretched thermoplastic polyester resin sheet in a state where no tension is applied to the stretched thermoplastic polyester resin sheet.

  That is, it is preferable to anneal so that the length of the annealed stretched thermoplastic polyester resin sheet is 1.0 or less of the length of the stretched thermoplastic polyester resin sheet before annealing.

  Therefore, when the stretched thermoplastic polyester resin sheet is continuously annealed while being moved in a heating chamber by a roll such as a pinch roll, the feed rate ratio of the stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to 1. It is preferable to anneal by setting it to be 0 or less.

  The heating method at the time of annealing is not particularly limited, and examples thereof include a method of heating with hot air or a heater.

  The time for annealing is not particularly limited and varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the annealing temperature, but is generally preferably 10 seconds or longer, more preferably 30 seconds to 60 minutes, and further preferably 1 to 20 Minutes.

  When the stretched thermoplastic polyester resin sheet has a large linear expansion coefficient, it expands and contracts greatly due to a temperature difference. In addition, since the stretched thermoplastic polyester resin sheet is laminated as a core material of the laminated molded body, it is preferable that the strength is high and the elastic modulus is 7 GPa or more.

  Two or more of the stretched thermoplastic polyester resin sheets may be laminated, and when laminated, they are preferably laminated so that their stretching directions are substantially the same.

  Any conventionally known method may be adopted as a method for laminating the stretched thermoplastic polyester resin sheets. However, the thermoplastic polyester resin of the drawn thermoplastic polyester resin sheet that has been drawn and stretched is highly oriented and has excellent strength and elastic modulus, but its crystallinity is low, so orientation is easy when heated at high temperatures. Since the elasticity is reduced and the elasticity is lowered, it is bonded with a hot melt type adhesive such as polyester or polyolefin having a melting point lower than the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet. Is preferred.

  The method of adhering with the hot melt adhesive is not particularly limited. For example, at least one of the methods in which the molten hot melt adhesive is applied to at least one stretched thermoplastic polyester resin sheet and the two are laminated and fused at the same time. A molten hot-melt adhesive is applied to the stretched thermoplastic polyester resin sheet and cooled to form a hot-melt adhesive layer and then laminated, or a sheet between two or more stretched thermoplastic polyester-based resin sheets And a method of heating a laminated body obtained by laminating a hot-melt adhesive in the form of a melt to melt and melt the hot-melt adhesive.

  In the latter method of melting and fusing the hot-melt adhesive, it is preferable to melt and fuse the hot-melt adhesive with an ultrasonic welder.

  As the method of fusing with the ultrasonic welder, any conventionally known method may be employed. For example, the stretched thermoplastic polyester resin sheet, the hot melt adhesive, the woven fabric and / or the nonwoven fabric, and the thermoplastic resin. There is a method in which a laminate such as a layer is passed between a horn and a knurl that are vibrated at a frequency of 15 to 40 kHz.

  FIG. 1 is an explanatory diagram showing an example of a method of forming two stretched thermoplastic polyester resin sheets with a hot melt adhesive using an ultrasonic welder.

  In the figure, reference numerals 1 and 1 denote stretched thermoplastic polyester resin sheets, and a hot melt type adhesive sheet 2 is laminated between the stretched thermoplastic polyester resin sheets 1 and 1 to form a laminate 10.

  The laminated body 10 is transported while being pressed by the horn 3 and the knurl 4 and is vibrated at a frequency of 15 to 40 kHz from the horn 3 so that the laminated body 10 is instantly hot due to frictional heat generated by the ultrasonic vibration transmitted from the horn 3. The melt type adhesive sheet 2 is heated and melted and fused.

  At this time, in order to fuse more efficiently, it is preferable that the gap between the horn 3 and the knurl 4 is set smaller than the thickness of the laminated body 10 and the laminated body 10 is fused while being pressed with the horn 3 and the knurl 4.

  In order to pressurize, it is preferable to connect an air cylinder, a hydraulic cylinder, etc. to the horn 3 and press the horn 3 against the knurl 4 through the laminate 10.

  In addition, a protrusion is formed on the surface of the knurl 4 so that it can be fused more efficiently. By changing the arrangement and shape of the protrusion, the arrangement of the fusion part and the pattern of the shape can be changed. Can do.

  2-6 is explanatory drawing which shows the example of the arrangement | sequence pattern of a fusion | fusion part. In the figure, 11 is a laminated molded body fused by an ultrasonic welder, A is the stretching direction of the stretched thermoplastic polyester resin sheet 1, and 5 is a fused site.

  Further, when fusing with an ultrasonic welder, in order to prevent the orientation state of the stretched thermoplastic polyester resin sheet 1 from being relaxed, tension is applied to the laminate 10 (stretched thermoplastic polyester resin sheet 1). Is preferably loaded.

  In addition, as a method of laminating different preferred stretched thermoplastic polyester resin sheets, 1 selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives. The method of making it adhere | attach with the type or two or more types of adhesive agents is mention | raise | lifted.

  Further, a woven fabric and / or a nonwoven fabric may be laminated between the stretched thermoplastic polyester resin sheets. When the woven fabric and / or the nonwoven fabric are laminated, the adhesion of the stretched thermoplastic polyester resin sheet is improved, and the tensile strength, impact resistance, and the like of the obtained laminated molded body are improved.

  The woven fabric and / or nonwoven fabric is not particularly limited, and any conventionally known woven fabric and nonwoven fabric can be used. For example, natural fibers such as cotton and suf, polyethylene fibers, polypropylene fibers, polyester fibers, nylon Examples thereof include woven fabrics and non-woven fabrics made of fibers such as fibers, vinylon fibers, acrylic fibers, aramid fibers, and the like, and fibers such as glass fibers and carbon fibers.

The basis weight and thickness of the woven fabric and the nonwoven fabric are not particularly limited, but generally the basis weight is preferably 10 to 500 g / m ² and the thickness is preferably 0.03 to 4 mm.

  The lamination method of the stretched thermoplastic polyester resin sheet and the woven fabric and / or the nonwoven fabric may be any conventionally known method, based on the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet. 1 selected from the group consisting of polyester, polyolefin and other hot melt adhesives having a low melting point, reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives Bonding with one or more types of adhesives is preferable because thermal relaxation of the stretched thermoplastic polyester resin sheet is suppressed.

  In order to improve the impact resistance by simply laminating the stretched thermoplastic polyester resin sheet and the woven fabric and / or non-woven fabric to improve the impact resistance, a hot melt having a melting point lower than that of the thermoplastic polyester resin is used. It is preferable that the woven fabric and / or the nonwoven fabric impregnated with the mold adhesive is laminated and bonded between the stretched thermoplastic polyester resin sheets.

  In this case, it is preferable to heat and melt the hot melt adhesive with an ultrasonic welder.

  And / or a woven fabric impregnated with one or more adhesives selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives, and / or A method of laminating and adhering a nonwoven fabric between stretched thermoplastic polyester resin sheets is also preferable.

  In the laminated molded body of the present invention, a thermoplastic resin layer is laminated on both surfaces of a stretched thermoplastic polyester resin sheet.

  The thermoplastic resin is laminated on both sides of the stretched thermoplastic polyester resin sheet to protect the stretched thermoplastic polyester resin sheet from cracking and cracking along the stretch direction due to impact, and the polyester resin It is intended to prevent the durability from lowering due to hydrolysis or deterioration by direct exposure to rainwater or sunlight.

  In addition, when the thermoplastic resin is melted and laminated on both sides of the stretched thermoplastic polyester resin sheet, the orientation of the stretched thermoplastic polyester resin sheet is determined when the melting point of the thermoplastic resin is higher than the melting point of the thermoplastic polyester resin. Is relaxed and the linear expansion coefficient is increased, and therefore, the thermoplastic resin is preferably a resin having a melting point lower than that of the thermoplastic polyester resin.

  Examples of the thermoplastic resin include hard vinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin, ABS resin, AES resin, styrene resin, AS resin, methyl methacrylate resin, polyethylene resin, and polypropylene resin. . Moreover, paints such as fluorine paint, acrylic silicon paint, and urethane paint may be used.

  In addition, when the thermoplastic resin is melted and laminated on both sides of the stretched thermoplastic polyester resin sheet, the orientation of the stretched thermoplastic polyester resin sheet is determined when the melting point of the thermoplastic resin is higher than the melting point of the thermoplastic polyester resin. Is relaxed and the linear expansion coefficient is increased, and therefore, the thermoplastic resin is preferably a resin that can be molded at a temperature lower than the melting point of the thermoplastic polyester resin.

  The thickness of the thermoplastic resin is not particularly limited and may be appropriately determined depending on the application. However, if the thickness is too thin, the protective effect is reduced, and if the thickness is increased, the thermoplastic resin becomes heavy and low linear expansion of the stretched thermoplastic polyester resin sheet. Since the effect of the coefficient is reduced, 0.1 to 3 mm is preferable.

  The method for laminating the thermoplastic resin layers on both sides of the stretched thermoplastic polyester resin sheet is not particularly limited, and any conventionally known laminating method may be employed, and examples thereof include the following methods.

(1) A method in which a thermoplastic resin is extrusion-coated on both sides of a stretched thermoplastic polyester resin sheet and laminated.

(2) A method in which a thermoplastic resin sheet is bonded to both surfaces of a stretched thermoplastic polyester resin sheet by hot pressing and laminated.

(3) Heat on both sides of the stretched thermoplastic polyester resin sheet with a hot melt adhesive such as polyester or polyolefin having a melting point lower than the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet. A method of adhering and laminating a plastic resin sheet.

(4) Adhere the thermoplastic resin sheet to both sides of the stretched thermoplastic polyester resin sheet with an adhesive such as reactive adhesive, epoxy adhesive, urethane adhesive, polyester adhesive, rubber adhesive, etc. Laminating method.

In order to increase the adhesive strength in the above method, the following method is employed.
(A) A method in which the surface of a stretched thermoplastic polyester resin sheet is shaved to form irregularities on the surface, and the thermoplastic resin is extrusion coated or pressed onto the thermoplastic resin sheet and laminated by an anchor effect.

(B) A large number of through-holes are formed in the stretched thermoplastic polyester resin sheet, and the thermoplastic resin is extrusion-coated, or the thermoplastic resin sheet is pressed, and the thermoplastic resin sheets on both sides are fused and laminated through the through-holes. how to.

(C) Polyester having a melting point lower than the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet and the melting point of the thermoplastic resin constituting the thermoplastic resin sheet, on the stretched thermoplastic polyester resin sheet, A method of laminating an adhesive layer made of a hot-melt type adhesive such as a polyolefin-based adhesive and then melt-extrusion-coating a thermoplastic resin on the adhesive layer, or pressing and heating a thermoplastic resin sheet for fusion bonding.

(D) From the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet and the melting point of the thermoplastic resin constituting the thermoplastic resin sheet between the stretched thermoplastic polyester resin sheet and the thermoplastic resin sheet. A method of laminating a sheet-like hot-melt adhesive such as a polyester or polyolefin having a low melting point, and then heating and fusing the hot-melt adhesive.
In this method, it is preferable that the above-described ultrasonic welder is used for fusion.

  A woven fabric and / or a nonwoven fabric may be laminated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin sheet. When the woven fabric and / or the nonwoven fabric are laminated, the adhesion between the stretched thermoplastic polyester resin sheet and the thermoplastic resin sheet is improved, and the tensile strength, impact resistance, and the like of the obtained laminated molded body are improved.

  The woven fabric and / or nonwoven fabric is not particularly limited, and any conventionally known woven fabric and nonwoven fabric can be used. For example, natural fibers such as cotton and suf, polyethylene fibers, polypropylene fibers, polyester fibers, nylon Examples thereof include woven fabrics and non-woven fabrics made of fibers such as fibers, vinylon fibers, acrylic fibers, aramid fibers, and the like, and fibers such as glass fibers and carbon fibers.

The basis weight and thickness of the woven fabric and the nonwoven fabric are not particularly limited, but generally the basis weight is preferably 10 to 500 g / m ² and the thickness is preferably 0.03 to 4 mm.

  As a method of laminating the stretched thermoplastic polyester resin sheet and the woven fabric and / or the nonwoven fabric and the woven fabric and / or the nonwoven fabric and the thermoplastic resin sheet, any conventionally known method may be employed. When laminating at a low temperature, hot-melt adhesives such as polyesters and polyolefins having a melting point lower than that of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet, reactive adhesives, epoxy It is preferable to bond with one or two or more types of adhesives selected from the group consisting of adhesives based on urethane, urethane adhesives, polyester adhesives, and rubber adhesives.

  In addition, stretched thermoplastic polyester resin sheet and woven fabric and / or non-woven fabric and woven fabric and / or non-woven fabric and thermoplastic resin sheet are laminated more easily and firmly bonded to improve impact resistance. A woven fabric and / or a nonwoven fabric impregnated with a hot-melt adhesive having a melting point of the polyester resin and a melting point lower than that of the thermoplastic resin constituting the thermoplastic resin sheet, and a stretched thermoplastic polyester resin sheet and a thermoplastic resin It is preferable to laminate and bond between sheets.

  In this case as well, it is preferable to laminate a woven fabric and / or nonwoven fabric impregnated with a hot melt adhesive on a stretched thermoplastic polyester resin sheet and a thermoplastic resin sheet, and then fuse them with an ultrasonic welder.

  Furthermore, in order to improve the impact resistance, the stretched thermoplastic polyester resin sheet and the woven fabric and / or nonwoven fabric and the woven fabric and / or nonwoven fabric and the thermoplastic resin sheet are laminated more easily and firmly bonded. Stretch woven and / or non-woven fabric impregnated with one or more adhesives selected from the group consisting of adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives You may laminate | stack and adhere | attach between a thermoplastic polyester-type resin sheet and a thermoplastic resin sheet.

  The laminated molded body can be molded into a predetermined shape by a molding method such as odd-shaped molding or bending, and a laminated molded body having a predetermined shape is obtained.

  Further, in order to improve the weather resistance and designability of the laminated molded body, a different resin layer may be laminated on the surface of the thermoplastic resin layer, or a paint may be applied.

  The laminated molded body of the present invention is suitably used as an exterior building material, particularly as a rain gutter.

  The structure of the laminated molded body of the present invention is as described above, and the thermoplastic resin is laminated on both sides of the drawn stretched thermoplastic polyester resin sheet. Excellent in workability, workability and productivity. Therefore, it can be suitably used as an exterior building material such as a rain gutter.

  To make a thick thermoplastic polyester resin sheet into a stretched sheet, it becomes a large-scale facility if the stretching machine can withstand the stretching load, so by laminating a thin thermoplastic polyester resin sheet, Equipment can be provided more economically.

  A stretched sheet of a thick thermoplastic polyester resin sheet is accelerated by crystallization due to uneven cooling during stretching, causing sink marks, resulting in uneven thickness and reduced quality. By laminating the resin sheets, the thickness accuracy is improved, and the laminated molded body has a uniform quality with no defects.

  In addition, the woven fabric and / or the non-woven fabric are laminated between the stretched thermoplastic polyester resin sheet and / or between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer, so that the tensile strength and impact resistance of the laminated molded body are obtained. Etc. improve more.

  Next, although an example of the present invention is given and explained in detail, the present invention is not limited to the following example.

Example 1
A polyethylene terephthalate sheet having a thickness of 1 mm (manufactured by Teijin Chemicals Limited, trade name “A-PET sheet FR”: limiting viscosity 0.7, crystallinity 4%) is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.) at 75 ° C. After preheating, a pair of rolls heated to 70 ° C. (roll interval 0.2 mm) was drawn at a speed of 2 m / min to obtain a drawn stretched polyethylene terephthalate sheet having a stretch ratio of about 5 times. The glass transition temperature of the polyethylene terephthalate sheet was 72 ° C.

  On both sides of the obtained stretched polyethylene terephthalate sheet, a polyester-based hot melt adhesive (trade name “Byron GM-920”, melting point 107 ° C., manufactured by Toyobo Co., Ltd.) was melt extrusion coated at a thickness of 0.03 mm. An adhesive laminated stretched polyethylene terephthalate sheet was obtained.

  A stretched polyethylene terephthalate sheet on which one adhesive is not laminated is sandwiched between the two obtained adhesive-laminated stretched polyethylene terephthalate sheets with the stretching direction aligned, and is passed between hot roll presses at 150 ° C. Thus, a polyethylene terephthalate laminate in which a hot-melt adhesive was laminated on both sides was obtained.

  A vinyl chloride resin sheet (made by Tokuyama Sekisui Co., Ltd., product number “TS1000R”) was laminated on both sides of the obtained polyethylene terephthalate laminate, and heated at 160 ° C. under a pressure of 1 MPa for 180 seconds. Pressed to obtain a laminated molded body in which vinyl chloride resin sheets were laminated on both sides of stretched polyethylene terephthalate.

It was 1.6 * 10 < ^-5 > / degreeC when the linear expansion coefficient of the obtained laminated molded object was measured based on JISK7197 .

(Comparative Example 1)
A polyethylene terephthalate sheet having a thickness of 1 mm (manufactured by Teijin Chemicals Ltd., trade name “A-PET sheet FR”: intrinsic viscosity 0.7) is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.) and preheated to 50 ° C. When a space between a pair of rolls heated to ° C. (roll interval: 0.2 mm) was drawn at a speed of 2 m / min, the polyethylene terephthalate sheet was cut at the roll part, and a drawn stretched polyethylene terephthalate sheet was not obtained. The glass transition temperature of the polyethylene terephthalate sheet was 72 ° C.

(Comparative Example 2)
A high-density polyethylene resin (manufactured by Nippon Polychem Co., Ltd.) having a weight average molecular weight (Mw) of 3.3 × 10 ⁵ and a melting point of 135 ° C. is supplied to the same-direction biaxial kneading extruder (manufactured by Plastic Engineering Laboratory), and the resin temperature is 200 After melt-kneading at 0 ° C., the melt-kneaded product was formed into a sheet having a thickness of 4.8 mm by a calender molding machine controlled at a roll temperature of 110 ° C. to obtain a polyethylene resin sheet.

  The obtained polyethylene resin sheet was rolled at a rolling ratio of 8.0 times using a rolling molding machine (manufactured by Sekisui Koki Co., Ltd.) heated to 120 ° C. to obtain a rolled sheet having a thickness of 0.6 mm.

  The obtained rolled sheet is subjected to 3.0-fold multi-stage stretching with a hot-air heating type multi-stage stretching apparatus (manufactured by Kyowa Engineering) heated to 110 ° C., with a total draw ratio of 24.0 times and a thickness of 0.2 mm. A stretched polyethylene resin sheet was obtained.

  An adhesive (trade name “EP001” manufactured by Cemedine Co., Ltd. was applied to both sides of the obtained stretched polyethylene resin sheet, and a vinyl chloride resin sheet having a thickness of 0.5 mm (product number “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.) was extruded. 1), and heat-pressed at 160 ° C. under a pressure of 1 MPa for 180 seconds to obtain a laminated molded body in which vinyl chloride resin sheets are laminated on both sides of a stretched polyethylene resin sheet.

  When the linear expansion coefficient of the obtained laminated molded body was measured in accordance with JIS K 7197, the stretched polyethylene resin sheet and the vinyl chloride resin sheet were peeled off and could not be measured.

It is explanatory drawing which shows an example of the method of making two extending | stretching thermoplastic polyester-type resin sheets by an ultrasonic welder with a hot-melt-type adhesive agent. It is explanatory drawing which shows an example of the arrangement pattern of the fusion | melting site | part of a laminated molded object. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated molded object differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated molded object differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated molded object differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated molded object differs.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stretched thermoplastic polyester resin sheet 2 Hot-melt-type adhesive sheet 3 Horn 4 Knurl 5 Fusion part 10 Laminated body 11 Laminated molded body

Claims (19)

Stretching by drawing a stretched thermoplastic polyester resin sheet through a pair of rolls at a temperature between the glass transition temperature of the thermoplastic polyester resin of −20 ° C. and the glass transition temperature of the thermoplastic polyester resin of + 20 ° C. A laminated molded article, wherein a thermoplastic resin layer is laminated on both surfaces of a thermoplastic polyester resin sheet (except when uniaxially stretched at a temperature higher than that of the roll) . The laminated molded article according to claim 1, wherein the amorphous polyester resin sheet has a crystallinity of less than 10% as measured by a differential scanning calorimeter. The laminated molded article according to claim 1 or 2, wherein a stretch ratio of the stretched thermoplastic polyester resin sheet is 2 to 9 times. The laminated molded body according to claim 1, 2 or 3, wherein two or more stretched thermoplastic polyester resin sheets are laminated such that the stretching directions are substantially the same. 5. Two or more stretched thermoplastic polyester resin sheets are bonded with a hot-melt adhesive having a melting point lower than that of the thermoplastic polyester resin. The laminated molded article described. 6. The laminated molded article according to claim 5, wherein the hot melt adhesive is fused by an ultrasonic welder. One or two or more types of stretched thermoplastic polyester resin sheets selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives The laminated molded article according to any one of claims 1 to 4, wherein the laminated molded article is bonded with an adhesive. The laminated molded body according to any one of claims 1 to 4, wherein a woven fabric and / or a nonwoven fabric are laminated between two or more stretched thermoplastic polyester resin sheets. A woven fabric and / or a nonwoven fabric impregnated with a hot melt adhesive having a melting point lower than that of the thermoplastic polyester resin is laminated and bonded between two or more stretched thermoplastic polyester resin sheets. The laminated molded body according to any one of claims 1 to 4, wherein The laminated molded article according to claim 9, wherein the hot melt adhesive is fused by an ultrasonic welder. One or two selected from the group consisting of a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive between two or more stretched thermoplastic polyester resin sheets The laminated molded body according to any one of claims 1 to 4, wherein a woven fabric and / or a nonwoven fabric impregnated with at least one kind of adhesive is laminated and bonded. The stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are bonded with a hot-melt adhesive having a melting point lower than the melting point of the thermoplastic polyester resin. The laminated molded article according to item. The laminated molded article according to claim 12, wherein the hot melt adhesive is fused by an ultrasonic welder. One or two types of stretched thermoplastic polyester resin sheet and thermoplastic resin layer selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives It is adhere | attached with the above adhesive agent, The laminated molded object of any one of Claims 1-11 characterized by the above-mentioned. The laminated molded article according to any one of claims 1 to 11, wherein a woven fabric and / or a nonwoven fabric is laminated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. A woven fabric and / or a nonwoven fabric impregnated with a hot melt adhesive having a melting point lower than that of the thermoplastic polyester resin is laminated and bonded between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. The layered molded article according to any one of claims 1 to 11, wherein The laminated molded article according to claim 16, wherein the hot melt adhesive is fused by an ultrasonic welder. Between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer, one kind selected from the group consisting of a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive, or The laminated formed article according to any one of claims 1 to 11, wherein a woven fabric and / or a nonwoven fabric impregnated with two or more kinds of adhesives are laminated and bonded. The laminated molded body according to any one of claims 1 to 18, wherein the laminated molded body is an exterior building material.

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